CN110364690A - Preparation method, negative electrode material and the lithium battery of negative electrode material - Google Patents
Preparation method, negative electrode material and the lithium battery of negative electrode material Download PDFInfo
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- CN110364690A CN110364690A CN201810308789.5A CN201810308789A CN110364690A CN 110364690 A CN110364690 A CN 110364690A CN 201810308789 A CN201810308789 A CN 201810308789A CN 110364690 A CN110364690 A CN 110364690A
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Abstract
The present invention provides the preparation method, negative electrode material and lithium battery of a kind of negative electrode material.The preparation method includes: that graphite is added in polyacrylonitrile solution, obtains suspension；The suspension separating treatment is obtained into solid phase；Solid phase described in step is added in coagulating bath, the presoma of polyacrylonitrile coated graphite is formed；Presoma pre-oxidation and carbonization treatment by the polyacrylonitrile coated graphite obtain negative electrode material.Not only simple grain is good for negative electrode material made from preparation method provided by the invention, but also is significantly improved using the first charge-discharge capacity and first charge discharge efficiency of lithium battery made from the negative electrode material.
Description
Technical field
The present invention relates to a kind of preparation method of negative electrode material, negative electrode material and lithium batteries.
Background technique
Lithium battery has that energy density is big, operating voltage is high, self-discharge rate is small, small in size, weight compared to lead-acid battery
Gently, the advantages such as have extended cycle life, and is widely used in various portable electronic devices and electric car.Currently, commercialized
Lithium battery is mainly graphite negative electrodes material, theoretical specific capacity 372mAh/g with negative electrode material.However, with to lithium battery
The raising of performance requirement needs to further increase battery capacity.Therefore, it improves the specific capacity of lithium battery negative electrode material, improve
Cycle performance and reduction irreversible capacity are the emphasis researched and developed for a long time.
Graphite is wide, cheap with source as lithium cell cathode material, charging/discharging voltage platform is low and reversible capacity
High advantage.But making the negative electrode material of battery with graphite, there is also following disadvantages: poor with solvent compatibility, large current density is electrical
Can be poor, because the total insertion of solvent molecule keeps graphite linings peeling-off when first charge-discharge, reduced so as to cause electrode life.It is common
Solution be that processing is modified to graphite material surface, modified starting point mainly has: one, change natural graphite table
Face structural property reduces the total insertion of irreversible loss and solvent molecule caused by because forming excessive SEI film due to causes
Graphite it is exfoliated；Two, change the structure and form of graphite, to improve the charge/discharge capacity of graphite.
It is described in JP1999246209A and " graphite and hard carbon particle is immersed in the pitch or coke that temperature is 10~300 DEG C
In oil, solvent separation and heat treatment are then carried out ", but this method is not only difficult to be formed in graphite and hard carbon surface with certain
The bitumen layer or tar layer of the high polymeric of thickness, and for natural graphite, the raising of structural stability will be by
Limitation.Yang Shuting et al. with resin modified obtain negative electrode material (Yang Shuting, Liu Lijun etc., modification graphite be used as cathode of lithium battery
The research of material, " functional material ", 2000, the 4th phase), chemical property is improved, and first charge-discharge efficiency reaches
94.9%, reversible specific capacity reaches 306mAh/g, and special capacity fade is only 8.2% after circulation 100 times.Scanning electron microscope analysis table
It is bright, the negative electrode material obtained with resin modified not only even particle size and corner angle are clearly demarcated, and also the clad formed is fine and close
Even, so that the surface of electrode made from the negative electrode material tends to uniformly, surface area suitably reduces, and chemical property is mentioned
It is high.However, resin is to need after cladding product is heat-treated through break process the shortcomings that cladding, break process may make clad structure
By different degrees of destruction, so that modified effect is deteriorated.
Summary of the invention
To solve the above problems, the present invention provides a kind of preparation method of negative electrode material, comprising the following steps: a) by graphite
It is added in polyacrylonitrile solution, obtains suspension；B) the step a) suspension is separated, obtains solid phase；C) by step b)
The solid phase is added in coagulating bath, forms the presoma of polyacrylonitrile coated graphite；D) by step c) the polyacrylonitrile packet
The presoma pre-oxidation and carbonization treatment for covering graphite obtain negative electrode material.The simple grain of the negative electrode material produced by the present invention
It is good, it is significantly improved using the first charge-discharge capacity and first charge discharge efficiency of lithium battery made from the negative electrode material.
As an implementation, the negative electrode material includes graphite and the hard carbon layer for being coated on the graphite outer surface,
Wherein, the hard carbon layer with a thickness of 50~800nm, the average grain diameter of the negative electrode material is 5~50 μm.
As an implementation, the hard carbon layer with a thickness of 50~500nm, the average grain diameter of the negative electrode material is
10~30 μm.
The thickness of hard carbon layer of the present invention can reduce because caused by forming excessive SEI film irreversible loss and
Graphite is exfoliated caused by the total insertion of electrolyte solvent molecule.In the present invention, if the hard carbon on negative electrode material surface
The thickness of layer is greater than the thickness of hard carbon layer of the present invention, will cause the conductivity decline of negative electrode material, influences the embedding lithium of battery
Effect and the reversible capacity for reducing lithium battery.
The average grain diameter of negative electrode material of the present invention enables to material to have preferable processing performance and charge and discharge for the first time
Electrical efficiency.In the present invention, it if the average grain diameter of negative electrode material is greater than the average grain diameter of negative electrode material of the present invention, will affect
The processing performance of negative electrode material is (that is, the pole piece made using the negative electrode material that average grain diameter is greater than negative electrode material of the present invention
The problem of being easily unevenly coated, and it is easy to appear particle after pole piece compacting, this pole piece, which is applied to, to be easy to make in lithium battery
At the problem of short circuit)；Meanwhile the average grain diameter of negative electrode material is bigger, surface area is smaller, lithium ion insertion entrance less and
The diffusion path of lithium ion is bigger；On cycle performance, the gap between negative electrode material particle is more, and contact effect is poor, electrode
Along with level enlargement deformation and volume expansion, as charge and discharge number increases, the passivation of SEI film in the telescopiny of lithium ion
It further increases, the conductive capability decline of electrode, so excessive partial size is unfavorable for the reversible insertion and abjection of lithium ion.If negative
The average grain diameter of pole material is less than the average grain diameter of negative electrode material of the present invention, will affect first charge-discharge efficiency, works as cathode
When the average grain diameter of material is smaller, since the specific surface area of negative electrode material increases, it is embedded in the solvation lithium ion of graphite linings altogether
Increase, resulting irreversible capacity loss increases, to reduce first charge-discharge efficiency, while the lesser cathode of partial size
The edge defect of material is more, the diffusional resistance of lithium ion is increased, and the particle of negative electrode material is smaller, with electrolyte contacts
Specific surface area it is bigger, it is more to form lithium ion consumed by SEI film during first charge-discharge, irreversible capacity loss
It is more.
As an implementation, the graphite in the negative electrode material and the mass ratio of the negative electrode material are 1.00:
1.01~1.00:1.13.
As an implementation, the graphite in the negative electrode material and the mass ratio of the negative electrode material are 1.00:
1.01~1.00:1.10.
As an implementation, the graphite can be natural graphite and/or artificial graphite.
As an implementation, the mass concentration of the polyacrylonitrile solution is 1%~10%.As a kind of embodiment party
Formula, the mass concentration of the polyacrylonitrile solution are 1%~6%.In the present invention, if the concentration of polyacrylonitrile solution is too low (low
In 1%), the thickness of the hard carbon layer of formation is less than the thickness of hard carbon layer of the present invention, the first charge-discharge of obtained lithium battery
Capacity is low and poor circulation；If the concentration of polyacrylonitrile solution is too high (being higher than 10%), the viscosity of polyacrylonitrile solution is big,
It is unfavorable for polyacrylonitrile solution coated graphite, so that the thickness of the hard carbon layer of negative electrode material obtained can be made to be greater than institute of the present invention
The first charge discharge efficiency of the thickness for stating hard carbon layer, obtained lithium battery is low.
As an implementation, the number-average molecular weight of the polyacrylonitrile is 70000~200000.As further excellent
Choosing, the number-average molecular weight of the polyacrylonitrile are 120000~150000.The number-average molecular weight of currently preferred polyacrylonitrile
The hard carbonation properties of polyacrylonitrile can preferably be played and improve the effect of hard carbon layer coated graphite.If the number of polyacrylonitrile
Average molecular weight is too small, will cause carbonization effect it is bad, it is not fine and close so as to cause the hard carbon layer of formation；And number-average molecular weight is too big,
It is unfavorable for polyacrylonitrile solution coated graphite under equivalent viscosities, so that the hard carbon layer of negative electrode material obtained can be made partially thick.
As an implementation, in step a), the solvent of the polyacrylonitrile solution is selected from dimethylformamide, diformazan
At least one of yl acetamide, dimethyl sulfoxide, ethylene carbonate and sulfolane.
As an implementation, in step a), graphite is added in polyacrylonitrile solution, stirs, obtains suspension.
As an implementation, the stirring is magnetic stirring apparatus or the blender stirring with agitating paddle.
As an implementation, the speed of agitator is 5~40r/min.As further preferred, the speed of agitator
For 10~30r/min.
As an implementation, the whipping temp is 20~50 DEG C, and the mixing time is 1~8h.As into one
Preferably, the whipping temp is 20~30 DEG C to step, and the mixing time is 2~5h.
As an implementation, in step b), described be separated into is separated using centrifuge centrifuge separation or stratification.
Extra polyacrylonitrile solution is separated, the solid phase for being coated with a small amount of polyacrylonitrile solution liquid film is obtained, which is conducive to
Progress coagulating bath is to obtain the presoma of the good polyacrylonitrile coated graphite of simple grain, the presoma of the polyacrylonitrile coated graphite
Through pre-oxidation and the good negative electrode material of the available simple grain of carbonization treatment, and the hard carbon layer of the negative electrode material with a thickness of 50
~800nm.
As an implementation, in step c), the group of the coagulating bath is divided into deionized water and/or polar solvent.Institute
It states and is diffused into one another between solvent and coagulating bath in polyacrylonitrile solution, conducive to the solvent that will be coated in the liquid film of graphite surface
Removing.
As an implementation, it is sub- to be selected from dimethylformamide, dimethyl acetamide, dimethyl for the polar solvent
At least one of sulfone, ethylene carbonate and sulfolane.
As an implementation, the group of the coagulating bath is divided into deionized water and polar solvent, and the polar solvent
Mass ratio with the deionized water is no more than 2:3.A certain proportion of polar solvent is added, in solidification, in liquid film
Solvent and coagulating bath between mutually diffusion velocity accelerate so that sovent diffusion of the liquid film close to graphite side is gone out, thus plus
Fast liquid film solidified inside ensure that the consistency, hardness and stability of the hard carbon layer formed after pre-oxidation, carbonization.On the other hand,
If the polar solvent accounting is too high, the solvent that will cause liquid film surface layer be easy to diffuse out and its internal sovent diffusion very
Slowly, the inside so as to cause the hard carbon layer of negative electrode material obtained is soft, structural instability, uses the lithium battery of the negative electrode material
Battery capacity and cycle performance on decline；Meanwhile if the polar solvent accounting is too high, it is also possible to clad can be made
Polyacrylonitrile have loss；If the polar solvent accounting is too low, exchange of solvent rate has almost no change.
As an implementation, in step c), the temperature of the coagulating bath is 15~60 DEG C.As further preferred,
The temperature of the coagulating bath is 20~40 DEG C.Coagulation bath temperature of the invention is capable of increasing expansion of the solvent in liquid film to coagulating bath
Diffusion rate of the deionized water in rate and coagulating bath to liquid film is dissipated, to accelerate the setting rate of liquid film.Due to solidifying
Gu rate increase, solidify it is more abundant, therefore liquid film solidify the polyacrylonitrile clad to be formed inside and outside portion's difference it is smaller, in,
The simple grain that external stress progressivelyes reach material after equilibrium is good, while the hard carbon layer for the negative electrode material being prepared is more equal
Even, lithium battery obtained gets a promotion in battery capacity and cycle performance.In the present invention, if coagulation bath temperature is too high, though
Solvent inside right liquid film can be diffused out quickly, but be easily destroyed structure, so that the hard carbon layer knot of negative electrode material obtained
Structure is unstable.When coagulation bath temperature is lower, the sovent diffusion inside liquid film is come out relatively slowly, and liquid film surface can quickly solidify shape
At relatively thin cortex, the cortex hardness is smaller, and internal relatively soft, therefore liquid film solidifies the polyacrylonitrile clad to be formed
Inside and outside portion's unbalance stress leads to the simple grain difference for the negative electrode material being prepared and the homogeneity difference of hard carbon layer and in irregular
Shape.
As an implementation, in step c), the setting time of the coagulating bath is 0.1~3h.As further excellent
Choosing, the setting time of the coagulating bath are 0.1~1h.The setting time of coagulating bath is too short, then the solvent in liquid film is not handed over completely
It swaps out, so that polyacrylonitrile internal layer does not solidify, takes out and be easy softening；Time is too long, then reduces production efficiency.
As an implementation, in step c), the step b) solid phase is added in coagulating bath, after solidification, is filtered
Separate, be dried to obtain the presoma of polyacrylonitrile coated graphite；
As an implementation, the temperature of the drying is 50~100 DEG C.As further preferred, the drying
Temperature is 70~100 DEG C.
As an implementation, the time of the drying is 2~10h.As further preferred, the time of the drying
For 4~10h.
As an implementation, in step d), the temperature of the pre-oxidation is 100~600 DEG C, the pre-oxidation when
Between be 1~10h.As further preferred, in step d), the temperature of the pre-oxidation is 100~400 DEG C, the pre-oxidation
Time is 2~8h.Selecting Pre oxidation is 100~600 DEG C, not only contribute to promote polyacrylonitrile cyclisation and crosslinking so as to
Carbonization later, so that the simple grain of the negative electrode material made is good, the battery capacity and cycle performance of lithium battery obtained
There is biggish promotion, and the compactness and uniformity of the hard carbon layer formed after carbonization can be improved.If Pre oxidation is low
In 100 DEG C, pre-oxidation speed is very slow, and required oxidization time is too long, and production efficiency is too low；And Pre oxidation is greater than 600
DEG C when, violent exothermic reaction occurs, easily leads to polyacrylonitrile and fuses, so that the simple grain of negative electrode material obtained
It is poor, and the hard carbon layer structural instability of negative electrode material, mechanical properties decrease, this negative electrode material, which is applied in lithium battery, to be led
The capacity and cycle performance for causing lithium battery obtained are deteriorated.
As an implementation, in step d), the heating rate control of the pre-oxidation is 1~10 DEG C/min.As
Further preferably, the heating rate control of the pre-oxidation is 3~7 DEG C/min.Cyclization, oxidation in preoxidation process is anti-
It should be all along with a large amount of heat release.Suitable heating rate is selected to be conducive to while promoting the cyclisation and crosslinking of polyacrylonitrile
The exothermic reaction in preoxidation process is mitigated, this not only contributes to subsequent carbonization, thus the simple grain of the negative electrode material made
Property it is good, the battery capacity and cycle performance of lithium battery obtained have biggish promotion, and can improve carbonization formed hard carbon
The compactness and uniformity of layer.If heat up too fast in preoxidation process, it is violent and adjoint to will lead to preoxidation process
Highly exothermic, this makes polyacrylonitrile be easy to happen fusing in pre-oxidation exothermic process, so that negative electrode material obtained
Simple grain it is poor, and the hard carbon layer structural instability of negative electrode material, mechanical properties decrease, this negative electrode material is applied to lithium electricity
The capacity and cycle performance that will lead to lithium battery obtained in pond are deteriorated.
As an implementation, in step d), the temperature of the carbonization treatment is 700~2100 DEG C, at the carbonization
The time of reason is 1~10h.As further preferred, the temperature of the carbonization treatment is 700~1500 DEG C, the carbonization treatment
Time be 3~8h.
As an implementation, in step d), the heating rate of the carbonization treatment is controlled in 1~10 DEG C/min.Make
To be further preferred, the heating rate of the carbonization treatment is controlled in 3~7 DEG C/min.With the carbonization of lesser heating rate, favorably
It uniformly and is sufficiently carried out in carburizing reagent, makes to be carbonized volatile ingredient in object and the ease of gas slowly that carburizing reagent generates
Out, to be conducive to form more initial micropore on hard carbon layer, the initial micropore on hard carbon layer can provide embedding lithium space；Favorably
In raising carbonization rate to guarantee covering amount；Be conducive to improve the intensity of carbonized product (i.e. hard carbon layer), carbonized product intensity
Increasing will inhibit graphite in negative electrode material to react with solvent in electrolyte, reduce the generation of graphite surface peeling phenomenon.
On the other hand, heating rate is too low, and it is low to will lead to production efficiency.
As an implementation, in step d), the carbonization treatment carries out in an inert atmosphere, and the inert atmosphere is
Nitrogen or argon gas.
It as an implementation, further include the negative electrode material classification for obtaining step d).
As an implementation, described to be classified as the classification of vibrating screening extension set.
As an implementation, the preparation method of the polyacrylonitrile solution includes that polyacrylonitrile is added to dimethyl
At least one of formamide, dimethyl acetamide, dimethyl sulfoxide, ethylene carbonate and sulfolane, and temperature be 20~
Stirring forms polyacrylonitrile solution under conditions of 110 DEG C.
As an implementation, the temperature control of the stirring is 40~80 DEG C.
As an implementation, the temperature of the stirring is controlled by heating water bath mode.
As an implementation, the heating rate control of the heating water bath is 1~10 DEG C/min.As further excellent
The heating rate control of choosing, the heating water bath is 3~6 DEG C/min.
As an implementation, the stirring is magnetic stirring apparatus or the blender stirring with agitating paddle.
As an implementation, the revolving speed of the stirring is 5~40r/min.As further preferred, the stirring
Revolving speed is 20~30r/min.
As an implementation, the time of the stirring is 1~10h.As further preferred, the time of the stirring
For 3~8h.
The present invention also provides a kind of negative electrode materials, are prepared by described in any item preparation methods among the above.
The present invention also provides a kind of lithium battery, including anode, electrolyte, diaphragm and cathode, the cathode is used as above-mentioned
The negative electrode material is prepared.
Detailed description of the invention
Fig. 1 is the SEM figure of negative electrode material made from the embodiment of the present invention one；
Fig. 2 is the SEM figure of negative electrode material section made from the embodiment of the present invention one.
Specific embodiment
Specific embodiment below expands detailed description to the present invention, however the present invention is not restricted to following implementation
Example.
The simple grain and structure of negative electrode material produced by the present invention are (that is, negative electrode material includes graphite and is coated on outside graphite
The hard carbon layer on surface) scanning electron microscope (manufacturer: Hitachi (HITACHI) can be passed through；Model: SU8010)；Amplify under room temperature
70.0K) verifying.Wherein, negative electrode material section the preparation method is as follows: negative electrode material powder and conducting resinl are mixed simultaneously
It dries, by optical microscopy centering after drying, ion dismembyator intermediate ion is put into after centering and cuts to obtain sample.
Embodiment one
The preparation of negative electrode material
1) 4g polyacrylonitrile powder is added in 196g dimethylformamide, magnetic agitation dissolve to obtain mass concentration be
2% polyacrylonitrile solution, wherein the number-average molecular weight of polyacrylonitrile is 130000, speed of agitator 25r/min, stirring temperature
Spending (heating water bath) is 30 DEG C, mixing time 3h.
2) graphite that 20g average grain diameter is 13.00 μm is added in the step 1) polyacrylonitrile solution, magnetic agitation
Suspension, speed of agitator 20r/min are obtained, whipping temp is 25 DEG C, mixing time 2h.
3) centrifuge separating step 2 is used) solid liquid phase of the suspension, obtain the solid phase of lower layer.
4) the step 3) solid phase is added in 300mL coagulating bath (deionized water), coagulation bath temperature is solid at 25 DEG C
Change 0.5 hour, after solidification, is filtered with Buchner funnel and filter membrane, and resulting substance will be filtered and be put into air dry oven,
The presoma of polyacrylonitrile coated graphite is obtained after toasting 3h under the conditions of 100 DEG C.
5) presoma of step 4) the polyacrylonitrile coated graphite is put into tube furnace pre-oxidized, carbonization treatment
Negative electrode material is obtained, Pre oxidation is 200 DEG C, preoxidation time 3h, and pre-oxidation heating rate is 3min/ DEG C, carbonization temperature
Degree is 1300 DEG C, carbonization time 3h, and carbonization heating rate is 3min/ DEG C.
As shown in Figure 1, the negative electrode material of the present embodiment preparation method preparation has preferable simple grain.
As shown in Fig. 2, the negative electrode material obtained includes graphite and the hard carbon layer for being coated on the graphite outer surface,
In, the hard carbon layer is 13.33 μm with a thickness of 150nm, the average grain diameter of the negative electrode material, the graphite and the cathode material
The mass ratio of material is 1:1.02.
Lithium battery (button cell) preparation
By negative electrode material, conductive agent and binder (sodium carboxymethylcellulose (CMC, Carboxymethylcellulose
Sodium)+butadiene-styrene rubber (SBR, Styrene Butadiene Rubber)) 80:12:8 in mass ratio is uniformly mixed, adds appropriate
Deionized water stirs 10min, is uniformly coated on copper foil with automatic film applicator, surface density is about 4.5mg/cm2.Air blast is dry
It after dry, is rolled on roll squeezer, the pole piece that diameter is 14mm is made, is put into 100 DEG C of baking 12h in vacuum oven.In glove box
Interior assembled battery, is anode with negative electrode material pole piece, and metal lithium sheet is to electrode, 1mol/L LiPF6Ethylene carbonate (EC)-
Diethyl carbonate (DEC) (volume ratio 3:7) is electrolyte.
Electric performance test
Test condition: current density 0.15mA/cm2, 0.01~1.5V of voltage, constant current charge-discharge；
Test result: discharge capacity is 373mAh/g for the first time, and first charge discharge efficiency is up to 93.5%.
Embodiment two
The preparation of negative electrode material and the difference of embodiment one are: in step 1), 2g polyacrylonitrile powder being added to
In 198g dimethylformamide, magnetic agitation obtains the polyacrylonitrile solution that mass concentration is 1%.
The negative electrode material obtained includes graphite and the hard carbon layer for being coated on the graphite outer surface, wherein described hard
Carbon layers having thicknesses are 50nm, and the average grain diameter of the negative electrode material is 13.12 μm, the mass ratio of the graphite and the negative electrode material
For 1:1.01.
The preparation of lithium battery (button cell) is the same as embodiment one；
Electric performance test
Test condition is the same as embodiment one；
Test result: discharge capacity is 366mAh/g for the first time, and first charge discharge efficiency is up to 92.3%.
Embodiment three
The preparation of negative electrode material and the difference of embodiment one are: in step 1), 20g polyacrylonitrile powder being dissolved in
In 180g dimethylformamide, magnetic agitation dissolves to obtain the polyacrylonitrile solution that mass concentration is 10%.
The negative electrode material obtained includes graphite and the hard carbon layer for being coated on the graphite outer surface, wherein described hard
Carbon layers having thicknesses are 800nm, and the average grain diameter of the negative electrode material is 14.80 μm, the quality of the graphite and the negative electrode material
Than for 1:1.13.
The preparation of lithium battery (button cell) is the same as embodiment one；
Electric performance test
Test condition is the same as embodiment one；
Test result: discharge capacity is 369mAh/g for the first time, and first charge discharge efficiency is up to 92.5%.
Example IV
The preparation of negative electrode material and the difference of embodiment one are: in step 1), the number-average molecular weight of polyacrylonitrile is
70000。
The negative electrode material obtained includes graphite and the hard carbon layer for being coated on the graphite outer surface, wherein described hard
Carbon layers having thicknesses are 130nm, and the average grain diameter of the negative electrode material is 13.30 μm, the quality of the graphite and the negative electrode material
Than for 1:1.02.
The preparation of lithium battery (button cell) is the same as embodiment one；
Electric performance test
Test condition is the same as embodiment one；
Test result: discharge capacity is 365mAh/g for the first time, and first charge discharge efficiency is up to 91.8%.
Embodiment five
The preparation of negative electrode material and the difference of embodiment one are: in step 1), the number-average molecular weight of polyacrylonitrile is
200000。
The negative electrode material obtained includes graphite and the hard carbon layer for being coated on the graphite outer surface, wherein described hard
Carbon layers having thicknesses are 180nm, and the average grain diameter of the negative electrode material is 13.41 μm, the quality of the graphite and the negative electrode material
Than for 1:1.03.
The preparation of lithium battery (button cell) is the same as embodiment one；
Electric performance test
Test condition is the same as embodiment one；
Test result: discharge capacity is 363mAh/g for the first time, and first charge discharge efficiency is up to 91.3%.
Embodiment six
The preparation of negative electrode material and the difference of embodiment one are: in step 4), the solid phase is added to 300mL coagulating bath
(deionized water and dimethyl sulfoxide, mass ratio 9:1).
The negative electrode material obtained includes graphite and the hard carbon layer for being coated on the graphite outer surface, wherein described hard
Carbon layers having thicknesses are 160nm, and the average grain diameter of the negative electrode material is 13.35 μm, the quality of the graphite and the negative electrode material
Than for 1:1.03.
The preparation of lithium battery (button cell) is the same as embodiment one；
Electric performance test
Test condition is the same as embodiment one；
Test result: discharge capacity is 375.5mAh/g for the first time, and first charge discharge efficiency is up to 94.8%.
Embodiment seven
The preparation of negative electrode material and the difference of embodiment one are: in step 4), the solid phase is added to 300mL coagulating bath
(deionized water and dimethyl sulfoxide, mass ratio 3:2).
The negative electrode material obtained includes graphite and the hard carbon layer for being coated on the graphite outer surface, wherein described hard
Carbon layers having thicknesses are 155nm, and the average grain diameter of the negative electrode material is 13.30 μm, the quality of the graphite and the negative electrode material
Than for 1:1.03.
The preparation of lithium battery (button cell) is the same as embodiment one；
Electric performance test
Test condition is the same as embodiment one；
Test result: discharge capacity is 376mAh/g for the first time, and first charge discharge efficiency is up to 93.9%.
Embodiment eight
The preparation of negative electrode material and the difference of embodiment one are: in step 4), the solid phase is added to 300mL coagulating bath
(deionized water and dimethyl sulfoxide, mass ratio 1:0.01).
The negative electrode material obtained includes graphite and the hard carbon layer for being coated on the graphite outer surface, wherein described hard
Carbon layers having thicknesses are 155nm, and the average grain diameter of the negative electrode material is 13.35 μm, the quality of the graphite and the negative electrode material
Than for 1:1.03.
The preparation of lithium battery (button cell) is the same as embodiment one；
Electric performance test
Test condition is the same as embodiment one；
Test result: discharge capacity is 373.5mAh/g for the first time, and first charge discharge efficiency is up to 93.7%.
Embodiment nine
The preparation of negative electrode material and the difference of embodiment one are: in step 4), coagulation bath temperature is 15 DEG C.
The negative electrode material obtained includes graphite and the hard carbon layer for being coated on the graphite outer surface, wherein described hard
Carbon layers having thicknesses are 143nm, and the average grain diameter of the negative electrode material is 13.29 μm, the quality of the graphite and the negative electrode material
Than for 1:1.02.
The preparation of lithium battery (button cell) is the same as embodiment one；
Electric performance test
Test condition is the same as embodiment one；
Test result: discharge capacity is 366mAh/g for the first time, and first charge discharge efficiency is up to 92.3%.
Embodiment ten
The preparation of negative electrode material and the difference of embodiment one are: in step 4), coagulation bath temperature is 60 DEG C.
The negative electrode material obtained includes graphite and the hard carbon layer for being coated on the graphite outer surface, wherein described hard
Carbon layers having thicknesses are 143nm, and the average grain diameter of the negative electrode material is 13.32 μm, the quality of the graphite and the negative electrode material
Than for 1:1.02.
The preparation of lithium battery (button cell) is the same as embodiment one；
Electric performance test
Test condition is the same as embodiment one；
Test result: discharge capacity is 364mAh/g for the first time, and first charge discharge efficiency is up to 92.5%.
Embodiment 11
The preparation of negative electrode material and the difference of embodiment one are: in step 4), curing time (coagulating bath time) is
0.1h。
The negative electrode material obtained includes graphite and the hard carbon layer for being coated on the graphite outer surface, wherein described hard
Carbon layers having thicknesses are 140nm, and the average grain diameter of the negative electrode material is 13.32 μm, the quality of the graphite and the negative electrode material
Than for 1:1.02.
The preparation of lithium battery (button cell) is the same as embodiment one；
Electric performance test
Test condition is the same as embodiment one；
Test result: discharge capacity is 367mAh/g for the first time, and first charge discharge efficiency is up to 91.8%.
Embodiment 12
The preparation of negative electrode material and the difference of embodiment one are: in step 4), curing time (coagulating bath time) is 3h.
The negative electrode material obtained includes graphite and the hard carbon layer for being coated on the graphite outer surface, wherein described hard
Carbon layers having thicknesses are 155nm, and the average grain diameter of the negative electrode material is 13.36 μm, the quality of the graphite and the negative electrode material
Than for 1:1.03.
The preparation of lithium battery (button cell) is the same as embodiment one；
Electric performance test
Test condition is the same as embodiment one；
Test result: discharge capacity is 371mAh/g for the first time, and first charge discharge efficiency is up to 92.9%.
Embodiment 13
The preparation of negative electrode material and the difference of embodiment one are: in step 5), Pre oxidation is 100 DEG C, pre-oxidation
Time is 10h, and pre-oxidation heating rate is 1min/ DEG C, and carburizing temperature is 700 DEG C, carbonization time 10h, and be carbonized heating rate
It is 1min/ DEG C.
The negative electrode material obtained includes graphite and the hard carbon layer for being coated on the graphite outer surface, wherein described hard
Carbon layers having thicknesses are 145nm, and the average grain diameter of the negative electrode material is 13.31 μm, the quality of the graphite and the negative electrode material
Than for 1:1.02.
The preparation of lithium battery (button cell) is the same as embodiment one；
Electric performance test
Test condition is the same as embodiment one；
Test result: discharge capacity is 368mAh/g for the first time, and first charge discharge efficiency is up to 92.2%.
Embodiment 14
The preparation of negative electrode material and the difference of embodiment one are: in step 5), Pre oxidation is 600 DEG C, pre-oxidation
Time is 1h, and pre-oxidation heating rate is 10min/ DEG C, and carburizing temperature is 2100 DEG C, carbonization time 1h, and be carbonized heating rate
It is 10min/ DEG C.
The negative electrode material obtained includes graphite and the hard carbon layer for being coated on the graphite outer surface, wherein described hard
Carbon layers having thicknesses are 143nm, and the average grain diameter of the negative electrode material is 13.29 μm, the quality of the graphite and the negative electrode material
Than for 1:1.02.
The preparation of lithium battery (button cell) is the same as embodiment one；
Electric performance test
Test condition is the same as embodiment one；
Test result: discharge capacity is 367mAh/g for the first time, and first charge discharge efficiency is up to 91.8%.
Embodiment 15
The preparation of negative electrode material
1) 4g polyacrylonitrile powder is added in 196g dimethylformamide, it is 2% that magnetic agitation, which obtains mass concentration,
Polyacrylonitrile solution, wherein the number-average molecular weight of polyacrylonitrile be 130000, speed of agitator 10r/min, whipping temp
(heating water bath) is 20 DEG C, mixing time 1h.
2) graphite that 20g average grain diameter is 13 μm is added in the step 1) polyacrylonitrile solution, magnetic agitation obtains
To suspension, speed of agitator 5r/min, whipping temp is 10 DEG C, mixing time 1h.
3) centrifuge separating step 2 is used) solid liquid phase of the suspension, obtain the solid phase of lower layer.
4) the step 3) solid phase is added in 300mL deionized water, coagulation bath temperature is that solidification 0.5 is small at 25 DEG C
When, it after solidification, is filtered with Buchner funnel and filter membrane, and resulting substance will be filtered and be put into air dry oven, in 50 DEG C of items
The presoma of polyacrylonitrile coated graphite is obtained after toasting 10h under part.
5) presoma of step 4) the polyacrylonitrile coated graphite is put into tube furnace pre-oxidized, carbonization treatment
Negative electrode material is obtained, Pre oxidation is 200 DEG C, preoxidation time 3h, and pre-oxidation heating rate is 3min/ DEG C, carbonization temperature
Degree is 1300 DEG C, carbonization time 3h, and carbonization heating rate is 3min/ DEG C.
The negative electrode material obtained includes graphite and the hard carbon layer for being coated on the graphite outer surface, wherein described hard
Carbon layers having thicknesses are 149nm, and the average grain diameter of the negative electrode material is 13.38 μm, the quality of the graphite and the negative electrode material
Than for 1:1.02.
The preparation of lithium battery (button cell) is the same as embodiment one；
Electric performance test
Test condition is the same as embodiment one；
Test result: discharge capacity is 373mAh/g for the first time, and first charge discharge efficiency is up to 93.2%.
Embodiment 16
The preparation of negative electrode material
1) 4g polyacrylonitrile powder is added in 196g dimethylformamide, it is 2% that magnetic agitation, which obtains mass concentration,
Polyacrylonitrile solution, wherein the number-average molecular weight of polyacrylonitrile be 130000, speed of agitator 10r/min, whipping temp
(heating water bath) is 110 DEG C, mixing time 10h.
2) graphite that 20g average grain diameter is 13 μm is added in the step 1) polyacrylonitrile solution, magnetic agitation obtains
To suspension, speed of agitator 40r/min, whipping temp is 30 DEG C, mixing time 8h.
3) centrifuge separating step 2 is used) solid liquid phase of the suspension, obtain the solid phase of lower layer.
4) the step 3) solid phase is added in 300mL deionized water, coagulation bath temperature is that solidification 0.5 is small at 25 DEG C
When, it after solidification, is filtered with Buchner funnel and filter membrane, and resulting substance will be filtered and be put into air dry oven, in 70 DEG C of items
The presoma of polyacrylonitrile coated graphite is obtained after toasting 4h under part.
5) presoma of step 4) the polyacrylonitrile coated graphite is put into tube furnace pre-oxidized, carbonization treatment
Negative electrode material is obtained, Pre oxidation is 200 DEG C, preoxidation time 3h, and pre-oxidation heating rate is 3min/ DEG C, carbonization temperature
Degree is 1300 DEG C, carbonization time 3h, and carbonization heating rate is 3min/ DEG C.
The negative electrode material obtained includes graphite and the hard carbon layer for being coated on the graphite outer surface, wherein described hard
Carbon layers having thicknesses are 151nm, and the average grain diameter of the negative electrode material is 13.36 μm, the quality of the graphite and the negative electrode material
Than for 1:1.02.
The preparation of lithium battery (button cell) is the same as embodiment one；
Electric performance test
Test condition is the same as embodiment one；
Test result: discharge capacity is 372.5mAh/g for the first time, and first charge discharge efficiency is up to 93.0%.
Embodiment 17
The preparation of negative electrode material and the difference of embodiment one are: in step 2), the average grain diameter of graphite is 4.68 μm.
The negative electrode material obtained includes graphite and the hard carbon layer for being coated on the graphite outer surface, wherein described hard
Carbon layers having thicknesses are 140nm, and the average grain diameter of the negative electrode material is 5.00 μm, the mass ratio of the graphite and the negative electrode material
For 1:1.02.
The preparation of lithium battery (button cell) is the same as embodiment one；
Electric performance test
Test condition is the same as embodiment one；
Test result: discharge capacity is 370mAh/g for the first time, and first charge discharge efficiency is up to 92.5%.
Embodiment 18
The preparation of negative electrode material and the difference of embodiment one are: in step 2), the average grain diameter of graphite is 49.61 μm.
The negative electrode material obtained includes graphite and the hard carbon layer for being coated on the graphite outer surface, wherein described hard
Carbon layers having thicknesses are 152nm, and the average grain diameter of the negative electrode material is 50.00 μm, the quality of the graphite and the negative electrode material
Than for 1:1.02.
The preparation of lithium battery (button cell) is the same as embodiment one；
Electric performance test
Test condition is the same as embodiment one；
Test result: discharge capacity is 374mAh/g for the first time, and first charge discharge efficiency is up to 93.7%.
Comparative example
20g graphite is put into air dry oven, 3h is toasted under the conditions of 100 DEG C, is put into tube furnace and is carried out in advance after baking
Oxidation, carbonization technique processing, wherein Pre oxidation is 200 DEG C, preoxidation time 3h, and pre-oxidation heating rate is 3min/
DEG C, carburizing temperature is 1300 DEG C, carbonization time 3h, and carbonization heating rate is 3min/ DEG C.
The preparation of lithium battery (button cell) is the same as embodiment one；
Electric performance test
Test condition is the same as embodiment one；
Test result: discharge capacity is 356mAh/g for the first time, and first charge discharge efficiency is up to 91%.
Claims (27)
1. a kind of preparation method of negative electrode material, comprising the following steps:
A) graphite is added in polyacrylonitrile solution, obtains suspension；
B) the step a) suspension is separated, obtains solid phase；
C) the step b) solid phase is added in coagulating bath, forms the presoma of polyacrylonitrile coated graphite；
D) the presoma pre-oxidation by step c) the polyacrylonitrile coated graphite and carbonization treatment obtain negative electrode material.
2. the preparation method of negative electrode material as described in claim 1, it is characterised in that: the negative electrode material includes graphite and packet
Overlay on the hard carbon layer of the graphite outer surface, wherein the hard carbon layer with a thickness of 50~800nm, the negative electrode material it is flat
Equal partial size is 5~50 μm.
3. the preparation method of negative electrode material as claimed in claim 2, it is characterised in that: the hard carbon layer with a thickness of 50~
500nm, the average grain diameter of the negative electrode material are 10~30 μm.
4. the preparation method of negative electrode material as claimed in claim 2, it is characterised in that: graphite and institute in the negative electrode material
The mass ratio for stating negative electrode material is 1.00:1.01~1.00:1.13.
5. the preparation method of negative electrode material as claimed in claim 4, it is characterised in that: graphite and institute in the negative electrode material
The mass ratio for stating negative electrode material is 1.00:1.01~1.00:1.10.
6. the preparation method of negative electrode material as described in claim 1, it is characterised in that: the graphite be natural graphite and/or
Artificial graphite.
7. the preparation method of negative electrode material as described in claim 1, it is characterised in that: the quality of the polyacrylonitrile solution is dense
Degree is 1%~10%.
8. the preparation method of negative electrode material as claimed in claim 7, it is characterised in that: the quality of the polyacrylonitrile solution is dense
Degree is 1%~6%.
9. the preparation method of negative electrode material as described in claim 1, it is characterised in that: the number-average molecular weight of the polyacrylonitrile
It is 70000~200000.
10. the preparation method of negative electrode material as claimed in claim 9, it is characterised in that: the equal molecule of the number of the polyacrylonitrile
Amount is 120000~150000.
11. the preparation method of negative electrode material as described in claim 1, it is characterised in that: in step a), the polyacrylonitrile is molten
The solvent of liquid in dimethylformamide, dimethyl acetamide, dimethyl sulfoxide, ethylene carbonate and sulfolane at least one
Kind.
12. the preparation method of negative electrode material as described in claim 1, it is characterised in that: in step c), the group of the coagulating bath
It is divided into deionized water and/or polar solvent.
13. the preparation method of negative electrode material as claimed in claim 12, it is characterised in that: the group of the coagulating bath be divided into from
Sub- water and polar solvent, and the polar solvent and the mass ratio of the deionized water are no more than 2:3.
14. the preparation method of negative electrode material as described in claim 12 or 13, it is characterised in that: the polar solvent is selected from two
At least one of methylformamide, dimethyl acetamide, dimethyl sulfoxide, ethylene carbonate and sulfolane.
15. the preparation method of negative electrode material as described in claim 1, it is characterised in that: in step c), the temperature of the coagulating bath
Degree is 15~60 DEG C.
16. the preparation method of negative electrode material as claimed in claim 15, it is characterised in that: the temperature of the coagulating bath be 20~
40℃。
17. the preparation method of negative electrode material as described in claim 1, it is characterised in that: in step c), the coagulating bath is coagulated
Gu the time is 0.1~3h.
18. the preparation method of negative electrode material as claimed in claim 17, it is characterised in that: the setting time of the coagulating bath is
0.1~1h.
19. the preparation method of negative electrode material as described in claim 1, it is characterised in that: in step c), step b) is described solid
It is added in coagulating bath, after solidification, filters the presoma for separating, being dried to obtain polyacrylonitrile coated graphite.
20. the preparation method of negative electrode material as described in claim 1, it is characterised in that: in step d), the temperature of the pre-oxidation
Degree is 100~600 DEG C.
21. the preparation method of negative electrode material as described in claim 1, it is characterised in that: in step d), the liter of the pre-oxidation
Warm speed control is 1~10 DEG C/min.
22. the preparation method of negative electrode material as described in claim 1, it is characterised in that: in step d), the carbonization treatment
Temperature is 700~2100 DEG C.
23. the preparation method of lithium battery negative electrode material as described in claim 1, it is characterised in that: in step d), the carbon
The time for changing processing is 1~10h.
24. the preparation method of negative electrode material as described in claim 1, it is characterised in that: in step d), the carbonization treatment
Heating rate is controlled in 1~10 DEG C/min.
25. the preparation method of negative electrode material as described in claim 1, it is characterised in that: in step d), the carbonization treatment exists
It is carried out in inert atmosphere, the inert atmosphere is nitrogen or argon gas.
26. a kind of negative electrode material is prepared by the preparation method as described in any one of claim 1-25.
27. a kind of lithium battery, including anode, electrolyte, diaphragm and cathode, the cathode uses as claimed in claim 26 negative
Pole material is prepared.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111276684A (en) * | 2020-02-17 | 2020-06-12 | 东南大学 | Preparation method and application of carbon-coated composite material |
| CN112225194A (en) * | 2020-09-24 | 2021-01-15 | 中国科学院化学研究所 | Hard carbon material and preparation method and application thereof |
| WO2021108987A1 (en) * | 2019-12-03 | 2021-06-10 | 宁德时代新能源科技股份有限公司 | Composite graphite material, secondary battery, device, and preparation method |
| CN114245942A (en) * | 2019-12-03 | 2022-03-25 | 宁德时代新能源科技股份有限公司 | Composite graphite material, preparation method thereof, secondary battery and device |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040227264A1 (en) * | 2003-05-16 | 2004-11-18 | Caisong Zou | Methods for fabricating improved graphite granules |
| CN1549362A (en) * | 2003-05-16 | 2004-11-24 | 比亚迪股份有限公司 | Method for producing modified graphite |
| CN1624955A (en) * | 2003-12-01 | 2005-06-08 | 上海杉杉科技有限公司 | Method for manufacturing carbon nagtive electrode material of lithium ion cell |
| TW200915638A (en) * | 2007-09-28 | 2009-04-01 | Panasonic Energy Taiwan Co Ltd | Composite graphite for lithium secondary cell and manufacturing method thereof |
| CN102610795A (en) * | 2011-01-20 | 2012-07-25 | 宁波宏远炭素工业有限公司 | Preparation method of lithium ion battery carbon cathode material coating layer |
| CN102931407A (en) * | 2012-11-01 | 2013-02-13 | 无锡东恒新能源材料有限公司 | Method for modifying natural graphite |
| CN103151497A (en) * | 2013-03-16 | 2013-06-12 | 无锡东恒新能源材料有限公司 | Preparation method of negative material for low-temperature lithium ion battery |
| CN103346305A (en) * | 2013-07-01 | 2013-10-09 | 华南师范大学 | Preparation and application of lithium battery silicon-carbon composite material taking synthetic graphite as carrier |
| CN104332616A (en) * | 2014-09-09 | 2015-02-04 | 刘剑洪 | Graphene coated graphite composite lithium ion battery negative material and its preparation method |
| CN104332630A (en) * | 2014-10-22 | 2015-02-04 | 深圳市贝特瑞新能源材料股份有限公司 | Surface coated graphite cathode material, preparation method of surface coated graphite cathode material, as well as lithium ion battery containing surface coated graphite cathode material |
| CN106684360A (en) * | 2017-01-20 | 2017-05-17 | 江西紫宸科技有限公司 | Carbon coating method of artificial graphite negative material, negative material and lithium ion battery |
| CN107681125A (en) * | 2016-08-02 | 2018-02-09 | 微宏动力系统（湖州）有限公司 | A kind of cathode material of lithium ion battery, its preparation method and lithium rechargeable battery |
| CN107732245A (en) * | 2017-10-20 | 2018-02-23 | 成都新柯力化工科技有限公司 | A kind of preparation method of hard carbon/graphene composite negative pole for lithium battery |
-
2018
- 2018-04-09 CN CN201810308789.5A patent/CN110364690B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040227264A1 (en) * | 2003-05-16 | 2004-11-18 | Caisong Zou | Methods for fabricating improved graphite granules |
| CN1549362A (en) * | 2003-05-16 | 2004-11-24 | 比亚迪股份有限公司 | Method for producing modified graphite |
| CN1624955A (en) * | 2003-12-01 | 2005-06-08 | 上海杉杉科技有限公司 | Method for manufacturing carbon nagtive electrode material of lithium ion cell |
| TW200915638A (en) * | 2007-09-28 | 2009-04-01 | Panasonic Energy Taiwan Co Ltd | Composite graphite for lithium secondary cell and manufacturing method thereof |
| CN102610795A (en) * | 2011-01-20 | 2012-07-25 | 宁波宏远炭素工业有限公司 | Preparation method of lithium ion battery carbon cathode material coating layer |
| CN102931407A (en) * | 2012-11-01 | 2013-02-13 | 无锡东恒新能源材料有限公司 | Method for modifying natural graphite |
| CN103151497A (en) * | 2013-03-16 | 2013-06-12 | 无锡东恒新能源材料有限公司 | Preparation method of negative material for low-temperature lithium ion battery |
| CN103346305A (en) * | 2013-07-01 | 2013-10-09 | 华南师范大学 | Preparation and application of lithium battery silicon-carbon composite material taking synthetic graphite as carrier |
| CN104332616A (en) * | 2014-09-09 | 2015-02-04 | 刘剑洪 | Graphene coated graphite composite lithium ion battery negative material and its preparation method |
| CN104332630A (en) * | 2014-10-22 | 2015-02-04 | 深圳市贝特瑞新能源材料股份有限公司 | Surface coated graphite cathode material, preparation method of surface coated graphite cathode material, as well as lithium ion battery containing surface coated graphite cathode material |
| CN107681125A (en) * | 2016-08-02 | 2018-02-09 | 微宏动力系统（湖州）有限公司 | A kind of cathode material of lithium ion battery, its preparation method and lithium rechargeable battery |
| CN106684360A (en) * | 2017-01-20 | 2017-05-17 | 江西紫宸科技有限公司 | Carbon coating method of artificial graphite negative material, negative material and lithium ion battery |
| CN107732245A (en) * | 2017-10-20 | 2018-02-23 | 成都新柯力化工科技有限公司 | A kind of preparation method of hard carbon/graphene composite negative pole for lithium battery |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021108987A1 (en) * | 2019-12-03 | 2021-06-10 | 宁德时代新能源科技股份有限公司 | Composite graphite material, secondary battery, device, and preparation method |
| CN113207315A (en) * | 2019-12-03 | 2021-08-03 | 宁德时代新能源科技股份有限公司 | Composite graphite material, secondary battery, device and preparation method |
| CN114245942A (en) * | 2019-12-03 | 2022-03-25 | 宁德时代新能源科技股份有限公司 | Composite graphite material, preparation method thereof, secondary battery and device |
| US11710822B2 (en) | 2019-12-03 | 2023-07-25 | Contemporary Amperex Technology Co., Limited | Composite graphite material, secondary battery, apparatus and preparation method thereof |
| CN113207315B (en) * | 2019-12-03 | 2024-05-10 | 宁德时代新能源科技股份有限公司 | Composite graphite material, secondary battery, device and preparation method |
| CN111276684A (en) * | 2020-02-17 | 2020-06-12 | 东南大学 | Preparation method and application of carbon-coated composite material |
| CN112225194A (en) * | 2020-09-24 | 2021-01-15 | 中国科学院化学研究所 | Hard carbon material and preparation method and application thereof |
| CN112225194B (en) * | 2020-09-24 | 2022-03-01 | 中国科学院化学研究所 | Hard carbon material and preparation method and application thereof |
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